Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams

ABSTRACT

White graft polymer dispersions in polyoxyalkylene polyether polyols are employed together with flame retardant compounds to prepare flame retardant polyurethane foams. The polymer dispersions employ less than 0.1 mole of induced unsaturation per mole of polyol mixture. Improved processes for the reparation of these polymer dispersions employ either isomerized maleate containing polyetherester polyols or polyetherester polyols prepared by reacting a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydride and an alkylene oxide in the presence of salts and oxides of divalent metals.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to low viscosity white graft polymerdispersions in polyoxyalkylene polyether polyols and flame retardantpolyurethane foams prepared therefrom. More particularly, the inventionrelates to graft polymer dispersions prepared by the improved processemploying free radical polymerization of an ethylenically unsaturatedmonomer or mixture of monomers in a polyol mixture containing less than0.1 mole of induced unsaturation per mole of polyol mixture. Thisimproved process yields stable, non-settling dispersions with graftpolymer contents of 30 percent by weight and higher employing monomermixtures which contain more than about 55 percent by weight styrene asthe comonomer. Further, the invention relates to an improved processemploying free radical polymerization in a polyetheresterpolyol-polyoxyalkylene polyether polyol mixture containing less tha 0.1mole of induced unsaturation per mole of polyol mixture wherein theunsaturated moiety is an isomerized maleate containing polyetheresterpolyol. Even more particularly the invention relates to an improvedprocess employing free radical polymerization in a polyol mixturecontaining polyetherester polyol-polyoxyalkylene polyether polyolmixture which was prepared by reacting a polyoxyalkylene polyetherpolyol, a polycarboxylic acid anhydride and an alkylene oxide in thepresence of an effective amount of a catalyst selected from the groupconsisting of salts and oxides of divalent metals.

2. Description of the Prior Art

The prior art, as evidenced by U.S. Pat. Nos. .[.3,652,658.]..Iadd.3,652,639.Iaddend.; 3,875,258; 3,950,317, and U.S. Pat. Nos. Re.28,715 and 29,014 teaches the preparation of graft polymer dispersionswhich are useful in the preparation of polyurethanes by thepolymerization of ethylenically unsaturated monomers in the presence ofpolyols. The above patents disclose various methods of preparing graftpolymer dispersions. U.S. Pat. No. 3,931,092 teaches the preparation ofpolymeric solids by polymerizing in the presence of a free-radicalinitiator and an organic solvent. The solvent concentration employed isfrom about 1 part to 19 parts by weight per part of thehydroxy-terminated organic compound which has a polymerizable carbondouble bond. U.S. Pat. No. 3,953,393 teaches the preparation of graftcopolymer dispersions by employing alkylmercaptan chain transferringagents at concentrations from 0.1 to 2 percent by weight based on theweight of vinyl monomer.

Stable dispersions of polymers in polyols have found broad commercialuse in the preparation of polyurethanes. The use of these dispersions,known in the trade as graft or polymer polyols, improves processing and,among other properties, the firmness of the polyurethane products, oftenexpressed as load bearing or modulus. There have been many attempts toimprove the products representing the present state of the art. Effortshave been directed towards increasing the amount of polymer which isdispersed in the polyol, the obvious benefit being that firmerpolyurethanes can be produced. Two major obstacles have been found: theviscosities of the resulting dispersions were too high and/or relativelyhigh levels of acrylonitrile had to be used in the monomer mixturesemployed.

The use of high levels (≧50 percent by weight) of acrylonitrile and,correspondingly, relatively low levels of the most common comonomer,styrene (≦50 percent) had two very undesirable effects. The resultingdispersions are tan to brown in color with a strong tendency to turnever darker in color during the highly exothermic polyurethane foamformation giving, for example, slab foams with a strong tendency toscorch. But even more undesirable, polyurethane foams made from theseproducts cannot be satisfactorily flame retarded to pass flammabilitytests which are standard in the industry.

As mentioned before, there have been attempts to prepare high polymer(≧30 percent) containing dispersions with acceptable viscosities. Theseproducts contain ratios of acrylonitrile to styrene of >50/50 and aretan colored. None of the prior art teaches that polymer dispersions inunsaturated polyols containing less than 0.1 mole of inducedunsaturation per mole of polyol mixture may be employed forflame-retardant polyurethane foams. Neither has the prior art taughtthat in situ free radical polymerizations may be conducted in apolyetherester polyol-polyoxyalkylene polyether polyol mixturecontaining less than 0.1 mole of induced unsaturation per mole of polyolmixture wherein the unsaturated moiety is an isomerized maleatecontaining polyetherester polyol. Also, the prior art is silent on thepreparation of polyetherester polyols, by the reaction of apolyoxyalkylene polyether polyol, a polycarboxylic acid anhydride, andan alkylene oxide, in the presence of a catalyst selected from the groupconsisting of salts and oxides of divalent metals.

SUMMARY OF THE INVENTION

It has been discovered that flame-retardant polyurethane foams may beprepared by employing graft polymer dispersions. These dispersions areprepared by an improved process employing free radical polymerization ofethylenically unsaturated monomer or monomers in a polyol mixturecontaining less than 0.1 mole of induced unsaturation per mole of polyolmixture. Furthermore, it has been found that improved dispersions may beprepared by employing radical polymerization in a polyetheresterpolyol-polyoxyalkylene polyether polyol mixture containing less than 0.1mole of induced unsaturation per mole of polyol mixture wherein theunsaturation moiety is an isomerized maleate containing polyetheresterpolyol. Still furthermore, it has been found that improved dispersionsmay be prepared by conducting the free radical polymerization in thepresence of a polyetherester polyol which was prepared by reacting apolyether polyol, a polycarboxylic acid anhydride, and an alkylene oxidein the presence of an effective amount of a catalyst selected from thegroup consisting of salts and oxides of divalent metals.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the improved process for the preparation of whitegraft polymer dispersions which are employed for the preparation offlame-retardant polyurethane foams, the improvement comprises conductingthe polymerization of an ethylenically unsaturated monomer or mixturesof monomers in the presence of an effective amount of a free-radicalinitiator in an unsaturated polyol mixture containing less than 0.1 moleof induced unsaturation per mole of polyol mixture. In anotherembodiment of the invention the polymerization of an ethylenicallyunsaturated monomer or mixture of monomers in the presence of aneffective amount of a free radical initiator in an unsaturationcontaining polyol mixture containing less than 0.1 mole of unsaturationper mole of polyol mixture employs an improved process which comprisesconducting the polymerization in a polyol mixture employing as part ofthe mixture a polyetherester polyol prepared by the reaction of apolyoxyalkylene polyether polyol with maleic anhydride and an alkyleneoxide. This polyetherester polyol is isomerized by methods well known bythose skilled in the art. These include heat, or isomerization catalystssuch as morpholine, dibutylamine, diethylamine, diethanolamine, thiolsand the like. In another improved process for the preparation of thesegraft polymer dispersions, the improvement consists of preparing apolyetherester polyol by the reaction of a polyoxyalkylene ether polyol,a polycarboxylic acid anhydride to form a half acid ester and analkylene oxide to obtain a product having an acid number of less than 5mg KOH/gram which comprises conducting the reaction between thepolyoxyalkylene polyether polyol and the anhydride and the followingreaction with the alkylene oxide in the presence of an effective amountof a catalyst selected from the group consisting of salts and oxides ofdivalent metals. The polyols having induced unsaturation are hereinafterreferred to as "macromers." Chain transfer agents may be employed asreaction moderators particularly at temperatures below 105° C. Thepolymerization reaction may be carried out at temperatures between 25°C. and 180° C., preferably between 80° C. and 135° C. The polyol mixturecontains less than 0.1 mole of unsaturation per mole of polyol mixtureand ranges from 0.001 to 0.09 mole of unsaturation.

The alkylene oxides which may be employed for the preparation of thepolyetherester polyols include ethylene oxide, propylene oxide, butyleneoxide, amylene oxide and mixtures of these oxides.

The graft polymer dispersions of this invention have viscosities lessthan 10,000 cps at 25° C. Preferably they have viscosities ranging from2000 to 8000 cps at 25° C.

Among those chain transfer agents which may be employed are as follows:acetic acid, bromoacetic acid, chloroacetic acid, ethyl dibromoacetate,iodoacetic acid, tribromoacetic acid, ethyl tribromoacetate,trichloroacetic acid, ethyl trichloroacetate, acetone,p-bromophenylacetonitrile, p-nitrophenylacetylene, allyl alcohol,2,4,6-trinitroaniline, p-ethynylanisole, 2,4,6-trinitroanisole,azobenzene, benzaldehyde, p-cyanobenzaldehyde, 2-butylbenzene,bromobenzene, 1,3,5-trinitrobenzene, benzochrysene, ethyltrinitrobenzoate, benzoin, benzonitrile, benzopyrene, tributylborane,1,4-butanediol, 3,4-epoxy-2-methyl-1-butene, t-butyl ether, t-butylisocyanide, 1-phenylbutyne, p-cresol, p-bromocumene, dibenzonaphthacene,p-dioxane, pentaphenyl ethane, ethanol, 1,1-diphenylethylene, ethyleneglycol, ethyl ether, fluorene, N,N-dimethylformamide, 2-heptene,2-hexene, isobutyraldehyde, diethyl bromomalonate,bromotrichloromethane, dibromoethane, diiodomethane, naphthalene,1-naphthol, 2-napthol, methyl oleate, 2,4,4-triphenyl-1-pentene,4-methyl-2-pentene, 2,6-diisopropylphenol, phenyl ether,phenylphosphine, diethylphosphine, dibutylphosphine, phosphorustrichloride, 1,1,1-tribromopropane, dialkyl phthalate, 1,2-propanediol,3-phosphinopropionitrile, 1-propanol, pyrocatechol, pyrogallol, methylstearate, tetraethylsilane, triethylsilane, dibromostilbene,α-bromostyrene, α-methylstyrene, tetraphenyl succinonitrile,2,4,6-trinitrotoluene, p-toluidine, N,N-dimethyl-p-toluidine,α-cyano-p-tolunitrile, α,α'-dibromo-p-xylene, 2,6-xylenol, diethyl zinc,dithiodiacetic acid, ethyl dithiodiacetic acid,4,4'-dithio-bisanthranilic acid, benzenethiol, o-ethoxybenzenethiol,2,2'-dithiobisbenzothiazole, benzyl sulfide, 1-dodecanethiol,ethanethiol, 1-hexanethiol, 1-napthalenethiol, 2-naphthalenethiol,1-octanethiol, 1-heptanethiol, 2-octanethiol, 1-tetradecanethiol,α-toluenethiol, isopropanol, 2-butanol, carbon tetrabromide and tertiarydodecyl mercaptan.

The chain transfer agents employed will depend on the particularmonomers or mixtures of monomers employed and the molar ratios of suchmixtures. The concentration of the chain transfer agent which isemployed may range from 0.1 to 10 percent by weight based on the weightof monomer.

Representative polyols essentially free from ethylenic unsaturationwhich may be employed in combination with the macromers of the inventionare well known to those skilled in the art. They are often prepared bythe catalytic condensation of an alkylene oxide or mixture of alkyleneoxides either simultaneously or sequentially with an organic compoundhaving at least two active hydrogen atoms, such as evidenced by U.S.Pat. Nos. 1,922,459; 3,190,927; and 3,346,557. Representative polyolsinclude polyhydroxyl-containing polyesters, polyoxyalkylene polyetherpolyols, polyhydroxy-terminated polyurethane polymers,polyhydroxyl-containing phosphorus compounds, and alkylene oxide adductsof polyhydric polythioesters, polyacetals, aliphatic polyols and thiols,ammonia, and amines including aromatic, aliphatic, and heterocyclicamines, as well as mixtures thereof. Alkylene oxide adducts of compoundswhich contain 2 or more different groups within the above-definedclasses may also be used, for example, amino alcohols which contain anamino group and a hydroxyl group. Also, alkylene oxide adducts ofcompounds which contain one SH group and one OH group as well as thosewhich contain an amino group and an SH group may be used. Generally,equivalent weight of the polyols will vary from 100 to 10,000,preferably from 1000 to 3000.

Any suitable hydroxy-terminated polyester may be used such are prepared,for example, from polycarboxylic acids and polyhydric alcohols. Anysuitable polycarboxylic acid may be used such as oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleicacid, fumaric acid, glutaconic acid, α-hydromuconic acid, β-hydromuconicacid, α-butyl-α-ethyl-glutaric acid, α,β-diethylsuccinic acid,isophthalic acid, terephthalic acid, hemimellitic acid, and1,4-cyclohexanedicarboxylic acid. Any suitable polyhydric alcohol,including both aliphatic and aromatic, may be used such as ethyleneglycol, propylene glycol, trimethylene glycol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol,1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol,1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,6-hexanetriol,α-methyl glycoside, pentaerythritol, and sorbitol. Also included withinthe term "polyhydric alcohol" are compounds derived from phenol such as2,2-bis(4-hydroxyphenyl)propane, commonly known as Bisphenol A.

The hydroxyl-containing polyester may also be a polyester amide such asis obtained by including some amine or amino alcohol in the reactantsfor the preparation of the polyesters. Thus, polyester amides may beobtained by condensing an amino alcohol such as ethanolamine with thepolycarboxylic acids set forth above or they may be made using the samecomponents that make up the hydroxyl-containing polyester with only aportion of the components being a diamine such as ethylene diamine.

Any suitable polyoxyalkylene polyether polyol may be used such as thepolymerization product of an alkylene oxide or a mixture of alkyleneoxides with a polyhydric alcohol. Any suitable polyhydric alcohol may beused such as those disclosed above for use in the preparation of thehydroxy-terminated polyesters. Any suitable alkylene oxide may be usedsuch as ethylene oxide, propylene oxide, butylene oxide, amylene oxide,and mixtures of these oxides. The polyoxyalkylene polyether polyols maybe prepared from other starting materials such as tetrahydrofuran andalkylene oxide-tetrahydrofuran mixtures; epihalohydrins such asepichlorohydrin; as well as aralkylene oxides such as styrene oxide. Thepolyoxyalkylene polyether polyols may have either primary or secondaryhydroxyl groups. Included among the polyether polyols arepolyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol,polytetramethylene glycol, block copolymers, for example, combinationsof polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutyleneand polyoxyethylene glycols, poly-1,4-oxybutylene and polyoxyethyleneglycols, and random copolymer glycols prepared from blends of two ormore alkylene oxides or by the sequential addition of two or morealkylene oxides. The polyoxyalkylene polyether polyols may be preparedby any known process such as, for example, the process disclosed byWurtz in 1859 and Encyclopedia of Chemical Technology, Vol. 7, pp.257-262, published by Interscience Publishers, Inc. (1951) or in U.S.Pat. No. 1,922,459. Polyethers which are preferred include the alkyleneoxide addition products of trimethylolpropane, glycerine,pentaerythritol, sucrose, sorbitol, propylene glycol, and2,2'-(4,4'-hydroxyphenyl)propane and blends thereof having equivalentweights of from 100 to 5000.

Suitable polyhydric polythioethers which may be condensed with alkyleneoxides include the condensation product of thiodiglycol or the reactionproduct of a dicarboxylic acid such as is disclosed above for thepreparation of the hydroxyl-containing polyesters with any othersuitable thioether glycol.

Polyhydroxyl-containing phosphorus compounds which may be used includethose compounds disclosed in U.S. Pat. No. 3,639,542. Preferredpolyhydroxyl-containing phosphorus compounds are prepared from alkyleneoxides and acids of phosphorous having a P₂ O₅ equivalency of from about72 percent to about 95 percent.

Suitable polyacetals which may be condensed with alkylene oxides includethe reaction product of formaldehyde or other suitable aldehyde with adihydric alcohol or an alkylene oxide such as those disclosed above.

Suitable aliphatic thiols which may be condensed with alkylene oxidesinclude alkanethiols containing at least two --SH groups such as1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, and1,6-hexanedithiol; alkene thiols such as 2-butene-1,4-dithiol; andalkyne thiols such as 3-hexyne-1,6-dithiol.

Suitable amines which may be condensed with alkylene oxides includearomatic amines such as aniline, o-chloroaniline, p-aminoaniline,1,5-diaminonaphthalene, methylene dianiline, the condensation productsof aniline and formaldehyde, and 2,3- 2,6-, 3,4-, 2,5-, and2,4-diaminotoluene; aliphatic amines such as methylamine,triisopropanolamine, ethylenediamine, 1,3-diaminopropane,1,3-diaminobutane, and 1,4-diaminobutane.

Also, polyols containing ester groups can be employed in the subjectinvention. These polyols are prepared by the reaction of an alkyleneoxide with an organic dicarboxylic acid anhydride and a compoundcontaining reactive hydrogen atoms. A more comprehensive discussion ofthese polyols and their method of preparation can be found in U.S. Pat.Nos. 3,585,185; 3,639,541 and 3,639,542.

The unsaturated polyols or macromers which are employed in the presentinvention may be prepared by the reaction of any conventional polyolsuch as those described above with an organic compound having bothethylenic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanateor epoxy group or they may be prepared by employing an organic compoundhaving both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride,or epoxy group as a reactant in the preparation of the conventionalpolyol. Representative of such organic compounds include unsaturatedmono- and polycarboxylic acids and anhydrides such as maleic acid andanhydride, fumaric acid, crotonic acid and anhydride, propenyl, succinicanhydride, acrylic acid, acryoyl chloride, hydroxy ethyl acrylate ormethacrylate and halogenated maleic acids and anhydrides, unsaturatedpolyhydric alcohols such as 2-butene-1,4-diol, glycerol allyl ether,trimethylolpropane allyl ether, pentaerythritol allyl ether,pentaerythritol vinyl ether, pentaerythritol diallyl ether, and1-butene-3,4-diol, unsaturated epoxides such as1-vinylcyclohexene-3,4-epoxide, butadiene monoxide, vinyl glycidylether(1-vinyloxy-2,3-epoxy propane), glycidyl methacrylate and3-allyloxypropylene oxide (allyl glycidyl ether). If a polycarboxylicacid or anhydride is employed to incorporate unsaturation into thepolyols, it is preferable to react the unsaturated polyol with analkylene oxide, preferably ethylene or propylene oxide, to replace thecarboxyl groups with hydroxyl groups prior to employment in the presentinvention. The amount of alkylene oxide employed in such as to reducethe acid number of the unsaturated polyol to about 5 or less.

The maleated macromers are isomerized at temperatures ranging from 80°C. to 120° C. for one-half hour to three hours in the presence of aneffective amount of an isomerization catalyst. The catalyst is employedat concentrations greater than 0.01 weight percent based on the weightof the macromer.

When preparing the polyetherester polyol employing the catalyst selectedfrom the group consisting of salts and oxides of divalent metals, theconcentration of catalyst which may be employed ranges from 0.005 to 0.5weight percent based on the weight of polyol mixture. The temperaturesemployed range from 75° C. to 175° C. The equivalent weight of themacromer may vary from 1000 to 10,000, preferably from 2000 to 6000.

Among the divalent metals which may be employed are: zinc acetate, zincchloride, zinc oxide, zinc neodecanoate, tin chloride, calciumnaphthenate, calcium chloride, calcium oxide, calcium acetate, coppernaphthenate, cadmium acetate, cadmium chloride, nickel chloride,manganese chloride, and manganese acetate.

Certain of the above-mentioned catalysts such as calcium naphthenatepromote the isomerization of the maleate to the fumarate structureduring the preparation of the macromer, while others such as zincchloride, which is an effective catalyst for the polymerization, inhibitthis isomerization.

As mentioned above, the graft polymer dispersions of the invention areprepared by the in situ polymerization, in the above-described polyolsof an ethylenically unsaturated monomer or a mixture of ethylenicallyunsaturated monomers. Representative ethylenically unsaturated monomerswhich may be employed in the present invention include butadiene,isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene,α-methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene,2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene,phenylstyrene, cycloexylstyrene, benzylstyrene, and the like;substituted styrenes such as cyanostyrene, nitrostyrene,N,N-dimethylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate,phenoxystyrene, p-vinylphenyl oxide, and the like; the acrylic andsubstituted acrylic monomers such as acrylonitrile, acrylic acid,methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, methylmethacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropylmthacrylate, octyl methacrylate, methacrylonitrile, ethylα-ethoxyacrylate, methyl α-acetaminoacrtylate, butyl acrylate,2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate,N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butylacrylamide,methacrylyl formamide, and the like; the vinyl esters, vinyl ethers,vinyl ketones, etc., such as vinyl acetate, vinyl butyrate, isopropenylacetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinylmethoxyacetate, vinyl benzoate, vinyltoluene, vinylnaphthalene, vinylmethyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butylethers, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether,3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl methylketone, vinyl ethyl ketone, vinyl phosphonates such as vinyl phenylketone, vinyl ethyl sulfone, N-methyl-N-vinyl acetamide,N-vinylpyrrolidone, vinyl imidazole, divinyl sulfoxide, divinyl sulfone,sodium vinylsulfonate, methyl vinylsulfonate, N-vinyl pyrrole, and thelike; dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid,fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethylmethacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, allylalcohol, glycol monoesters of itaconic acid, vinyl pyridine, and thelike. Any of the known polymerizable monomers can be used and thecompounds listed above are illustrative and not restrictive of themonomers suitable for use in this invention. Preferably, the monomer isselected from the group consisting of acrylonitrile, styrene andmixtures thereof.

The amount of ethylenically unsaturated monomer employed in thepolymerization reaction is generally from 25 percent to 60 percent,preferably from 30 percent to 45 percent, based on the total weight ofthe product. The polymerization occurs at a temperature between about25° C. and 180° C., preferably from 80° C. to 135° C. It is preferredthat at least 55 to 100 weight percent of the monomer employed isstyrene or 4-methylstyrene.

Illustrative polymerization initiators which may be employed are thewell-known free radical types of vinyl polymerization initiators such asthe peroxides, persulfates, perborates, percarbonates, azo compounds,etc. These include hydrogen peroxide, dibenzoyl peroxide, acetylperoxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butylperoxide, lauroyl peroxide, butyryl peroxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide,diacetyl peroxide, di-α-cumyl peroxide, dipropyl peroxide, diisopropylperoxide, isopropyl-t-butyl peroxide, butyl-t-butyl peroxide, difuroylperoxide, bis(triphenylmethyl) peroxide, bis(p-methoxybenzoyl)peroxide,p-monomethoxybenzoyl peroxide, rubene peroxide, ascaridol, t-butylperoxybenzoate, diethyl peroxyterephthalate, propyl hydroperoxide,isopropyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide,cyclohexyl hydroperoxide, trans-decalin hydroperoxide, α-methylbenzylhydroperoxide, α-methyl-α-ethyl benzyl hydroperoxide, tetralinhydroperoxide, triphenylmethyl hydroperoxide, diphenylmethylhydroperoxide, α,α'-azobis-(2-methyl heptonitrile),1,1'-azo-bis(cyclohexane carbonitrile), 4,4'-azobis(4-cyanopentanoicacid), 2,2'-azobis(isobutyronitrile), 1-t-butylazo-1-cyanocyclohexane,persuccinic acid, diisopropyl peroxy dicarbonate,2,2'-azobis(2,4-dimethylvaleronitrile),2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,2,2'-azobis-2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane,1-t-amylazo-1-cyanocyclohexane,2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile,2,2'-azobis-2-methylbutyronitrile, 2-t-butylazo-2-cyano-4-methylpentane,2-t-butylazo-2-isobutyronitrile, to butylperoxyisopropyl carbonate andthe like; a mixture of initiators may also be used. The preferredinitiators are 2,2'-azobis(2-methylbutyronitrile),2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile),2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylazo-2-cyano-butane andlauroyl peroxide. Generally, from about 0.1 percent to about 10 percent,preferably from about 1 percent to about 4 percent, by weight ofinitiator based on the weight of the monomer will be employed in theprocess of the invention.

The polyurethane foams employed in the present invention are generallyprepared by the reaction of a graft polymer dispersion with an organicpolyisocyanate in the presence of a blowing agent and optionally in thepresence of additional polyhydroxyl-containing components,chain-extending agents, catalysts, surface-active agents, stabilizers,dyes, fillers and pigments. Suitable processes for the preparation ofcellular polyurethane plastics are disclosed in U.S. Pat. No. Re. 24,514together with suitable machinery to be used in conjunction therewith.When water is added as the blowing agent, corresponding quantities ofexcess isocyanate to react with the water and produce carbon dioxide maybe used. It is possible to proceed with the preparation of thepolyurethane plastics by a prepolymer technique wherein an excess oforganic polyisocyanate is reacted in a first step with the polyol of thepresent invention to prepare a prepolymer having free isocyanate groupswhich is then reacted in a second step with water and/or additionalpolyol to prepare a foam. Alternatively, the components may be reactedin a single working step commonly known as the "one-shot" technique ofpreparing polyurethanes. Furthermore, instead of water, low boilinghydrocarbons such as pentane, hexane, heptane, pentene, and heptene; azocompounds such as azohexahydrobenzodinitrile; halogenated hydrocarbonssuch as dichlorodifluoromethane, trichlorofluoromethane,dichlorodifluoroethane, vinylidene chloride, and methylene chloride maybe used as blowing agents.

Organic polyisocyanates which may be employed include aromatic,aliphatic, and cycloaliphatic polyisocyanates and combinations thereof.Representative of these types are the diisocyanates such as m-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate,mixtures of 2,4- and 2,6-toluene diisocyanate, hexamethylenediisocyanate, tetramethylene diisocyanate, cyclohexane-1,4-diisocyanate,hexahydrotoluene diisocyanate (and isomers),naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate,4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate,3,3'-dimethoxy-4,4'-biphenyl diisocyanate,3,3'-dimethyl-4,4'-biphenyldiisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; thetriisocyanates such as 4,4',4"-triphenylmethane triisocyanate, andtoluene 2,4,6-triisocyanate; and the tetraisocyanates such as4,4'-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate and polymericpolyisocyanates such as polymethylene polyphenylene polyisocyanate.Especially useful due to their availability and properties are toluenediisocyanate, 4,4'-diphenylmethane diisocyanate and polymethylenepolyphenylene polyisocyanate.

Crude polyisocyanates may also be used in the compositions of thepresent invention, such as crude toluene diisocyanate obtained by thephosgenation of a mixture of toluene diamines or crude diphenylmethaneisocyanate obtained by the phosgenation of crude diphenylmethanediamine. The preferred or crude isocyanates are disclosed in U.S. Pat.No. 3,215,652.

As mentioned above, the graft polyols may be employed along with anotherpolyhydroxyl-containing component commonly employed in the art. Any ofthe polyhydroxyl-containing components which are described above for usein the preparation of the graft polyols may be employed in thepreparation of the polyurethane foams useful in the present invention.

Chain-extending agents which may be employed in the preparation of thepolyurethane foams include those compounds having at least twofunctional groups bearing active hydrogen atoms such as water,hydrazine, primary and secondary diamines, amino alcohols, amino acids,hydroxy acids, glycols, or mixtures thereof. A preferred group ofchain-extending agents includes water, ethylene glycol, 1,4-butanedioland primary and secondary diamines which react more readily with theprepolymer than does water such as phenylene diamine,1,4-cyclohexane-bis-(methylamine), ethylenediamine, diethylenetriamine,N-(2-hydroxypropyl)ethylenediamine,N,N'-di(2-hydroxypropyl)ethylenediamine, piperazine, and2-methylpiperazine.

Any suitable catalyst may be used including tertiary amines such as, forexample, triethylenediamine, N-methylmorpholine, N-ethylmorpholine,diethylethanolamine, N-cocomorpholine,1-methyl-4-dimethylaminoethylpiperazine, 3-methoxypropyldimethylamine,N,N,N'-trimethylisopropyl propylenediamine,3-diethylaminopropyldiethylamine, dimethylbenzylamine, and the like.Other suitable catalysts are, for example, stannous chloride, dibutyltindi-2-ethyl hexanoate, stannous oxide, as well as other organometalliccompounds such as are disclosed in U.S. Pat. No. 2,846,408.

A surface-active agent is generally necessary for production of highgrade polyurethane foam according to the present invention, since in theabsence of same, the foams collapse or contain very large uneven cells.Numerous surface-active agents have been found satisfactory. Nonionicsurface active agents are preferred. Of these, the nonionicsurface-active agents such as the well-known silicones have been foundparticularly desirable. Other surface-active agents which are operative,although not preferred, include polyethylene glycol ethers of long chainalcohols, tertiary amine or alkanolamine salts of long chain alkyl acidsulfate esters, alkyl sulfonic esters, and alkyl arylsulfonic acids.

It has been found in the preparation of the flame retardant polyurethanefoam products which have incorporated therein the graft polymerdispersions of the invention that less flame retardant compound isnecessary to impart flame retardency. Among the flame retardants whichmay be employed are: pentabromodiphenyl oxide, dibromopropanol,tris(β-chloropropyl)phosphate, 2,2-bis(bromoethyl) 1,3-propanediol,tetrakis(2-chloroethyl)ethylene diphosphate,tris(2,3-dibromopropyl)phosphate, tris(β-chloroethyl)phosphate,tris(1,2-dichloropropyl)phosphate, bis-(2-chloroethyl)2-chloroethylphosphonate, molybdenum trioxide, ammonium molybdate,ammonium phosphate, pentabromodiphenyloxide, tricresyl phosphate,hexabromocyclododecane and dibromoethyl-dibromocyclohexane. Theconcentrations of flame retardant compounds which may be employed rangefrom 5 to 25 parts per 100 parts of polyol mixture.

The following examples illustrate the nature of the invention. All partsare by weight unless otherwise stated. In the examples, the physicalproperties of the polyurethane foam were determined by the followingASTM tests:

Density--D1622-63

Tensile strength--D1623-72

Elongation--D412

Split Tear--D470

Compression Set--D395

Compression Load--D1564

Humid Aging--D1564

The following abbreviations are employed in the examples below:

Polyol A is a trimethylolpropane, propylene oxide, ethylene oxide adductcontaining 15 percent ethylene oxide, and a hydroxyl number of 25.

Polyol B is a glycerine, propylene oxide, ethylene oxide adductcontaining 12.5 percent ethylene oxide, and a hydroxyl number of 50.

Polyol C is a glycerine, propylene oxide, ethylene oxide adductcontaining 18.5 percent ethylene oxide, having a hydroxyl number of 35.

Polyol D is Polyol A containing 0.5 mole of unsaturation per mole ofpolyol.

Polyol E is Polyol A containing 0.7 mole of unsaturation per mole ofpolyol.

Polyol F is glycerine, ethylene oxide, propylene oxide adduct containing6 percent ethylene oxide having a reduced unsaturation of 0.3 mole permole of polyol, containing 36 weight percent of 3:1acrylonitrile:styrene based on the total weight of the polymer andhaving a hydroxyl number of 32.5.

Polyol G see procedure D.

Polyol H is a glycerine, ethylene oxide propylene oxide adductcontaining 16.5 percent ethylene oxide and having a hydroxyl number of35.

Polyol I see procedure E.

Polyol J see procedure B.

Catalyst A--zinc neodeconate as ppm zinc.

Catalyst B--calcium naphthenate as ppm calcium.

Catalyst C--copper naphthenate as ppm copper.

Catalyst D--cobalt naphthenate as ppm cobalt

Initiator A--2,2'-azobis(2-methylbutyronitrile)

DE-71 is pentabromodiphenyl oxide manufactured by Great Lakes Chemicals.

Thermolin 101 is tetrakis(2-chloroethyl)ethylene diphosphate.

Reactant Blue X-44 is a dye manufacture by Milliken, Inc.

L-5720 is a silicone surfactant manufactured by Union Carbon and CarbideCorporation.

DABCO TL is an amine catalyst manufactured by Air Products, Inc.

T-10 is an organo tin catalyst manufactured by M&T Chemicals, Inc.

DOP is dioctylphthalate.

TDI is toluene diisocyanate.

L-5043 is a silicone surfactant manufactured by Dow Corning Corporation.

T-12 is dibutyltin dilaurate

DABCO 33LV is a 33 percent solution of triethylene diamine in 67 percentdipropylene glycol.

NIAX A-1 is an amine catalyst manufactured by Union Carbon and CarbideCorporation.

AN is acrylonitrile

Sty is styrene

Antiblaze 19 reputedly has the structure ##STR1## wherein x is equal to0 or 1.

Procedure A

Charges:

The following charges were employed in examples 1 through 17 except asnoted otherwise in Table I.

2000 gm Polyol A

30.6 gm maleic anhydride (0.8 equivalents per mole of Polyol A)

10 gm catalyst B 200 ppm calcium

96 gm ethylene oxide (0.01 percent maximum water)

A 3-liter round-bottom flask with a stirrer, thermometer and gas inletwas charged with polyol A, maleic anhydride and calcium naphthenate. Thecontents were heated to 125° C. and allowed to react for 1 hour. Thisintermediate was transferred to a 1-gallon steam heated stainless steelautoclave. After heating to 125° C. and pressurizing the reactor to 34psig with nitrogen, ethylene oxide was added during 1 hour and themixture was reacted for 8 hours. The product was isolated afterdischarging by stripping the volatiles at 105° C. for 1 hour at <10 mmHg. This product is designated as polyol D.

Procedure B

Charges:

To reactor:

50 g polyol D

925 g polyol B

2.0 g initiator A

Stream #1:

260 g acrylonitrile

790 g styrene

13.5 g 1-dodecanethiol

Stream #2:

975 g polyol B

10.5 g initiator A

Reaction Conditions: reaction temperature, 90° C.; monomer additiontime, 210 minutes; polyol initiator addition time, 220 minutes; reactiontime, 30 minutes; 300 rpm stirring.

The reactor charges were added to a 5-liter 4-neck flask fitted with astirrer, nitrogen inlet, addition tube, water condenser and thermowell.After heating the polyol reaction mixture to 90° C. and holding for 30minutes under nitrogen, the streams #1 and #2 were added through aKenics static mixer over the specified time period. Upon completion ofstream #1 addition, the reaction mixture was heated to 110° C. andreacted for the specified time. After the reaction period was completed,the reaction mixture was vacuum stripped for 30 minutes at 115° C. and 1mm Hg. The polyol from this procedure is designated as polyol J.

Procedure C

Charges:

400 lbs. polyol A

7.72 lbs. maleic anhydride

17.24 lbs. ethylene oxide

The indicated amount of polyol A was charged to a clean, dry, nitrogenpurged 90-gallon reactor, sealed and heated to 110° C. The polyol wasthen flash stripped at less than 10 mm Hg into a clean, dry 60-gallonreactor. Stripping was continued until the residual water level had beenreduced to 0.01 weight percent. After stripping was completed, maleicanhydride was added to the polyol, the reaction mixture was padded with34 psi nitrogen and then heated to 150° C. After reacting for 4 hours,excess ethylene oxide was added over 5 hours at 150° C. This reactionmixture was allowed to react 8 to 12 hours or until the acid number haddropped below 0.2 mg KOH/g. The mixture was then stripped to removeexcess ethylene oxide. This product was designated as polyol E.

Procedure D

Charges:

To reactor:

10.67 lbs. polyol E

93.33 lbs. polyol B

0.053 lbs. morpholine

0.21 lb. initiator A

Stream #1:

28.0 lbs. acrylonitrile

84.0 lbs. styrene

1.12 lbs. 1-dodecanethiol

Stream #2:

104.0 lbs. polyol B

1.12 lbs. initiator A

Reaction Conditions: reaction temperature 90° C.; monomer addition time,210 minutes; polyol-initiator addition time, 220 minutes; reaction time,30 minutes.

The reactor charges were added under a nitrogen atmosphere to a50-gallon reactor. After heating the polyol reaction mixture to 90° C.and holding for 30 minutes, streams #1 and #2 were added through aKenics static mixer over the specified time period. Upon completion ofstream #1 addition, the reaction mixture was heated to 110° C. andreacted for the specified time. After the reaction period was completed,the reaction mixture was vacuum stripped for 3 hours at 125° C. and 5 mmHg. This product is designated as polyol G.

Procedure E

Charges:

To reactor:

85.3 lbs. polyol C

26.7 lbs. polyol A

0.19 lbs. initiator A

Stream #1:

24 lbs. acrylonitrile

72 lbs. styrene

0.96 lb. 1-dodecanethiol

Stream #2:

112.0 lbs. polyol C

0.96 lb. initiator A

Reaction Conditions: reaction temperature, 90° C.; monomer additiontime, 180 minutes; polyol-initiator addition time, 190 minutes; reactiontime, 30 minutes.

The same reaction procedure was used here as in procedure D.

This product is designated polyol I.

EXAMPLES 1-17

The products of these examples were prepared employing variouscatalysts, at various concentrations and at variable maleic anhydridecontents using procedure A.

                                      TABLE I                                     __________________________________________________________________________         Maleic      Catalyst                                                          Anhydride,  Level,         Saponification                                                                       Unsaturation                                                                         Viscosity                       Examples                                                                           Equivalents*                                                                         Catalyst                                                                           ppm  OH No.                                                                             Acid No.                                                                           No.    mole/mole**                                                                          cps, 25° C.              __________________________________________________________________________    1    0.8    A    800  25.5 0.57 22.2   0.6    11,900                          2    0.8    B    800  25.2 0    13.8   0.4    12,200                          3    0.8    C    800  22.2 1.3  18.6   0.6     2,760                          4    0.8    D    800  22.5 0.05 15.6   0.35   15,250                          5    0.8    B    800  26.3 0.22 15.1   0.45    9,425                          6    1.0    B    800  21.6 0    19.2   0.40   17,290                          7    1.5    B    800  23.9 0    27.1   --     100,000                         8    0.8    B    400  24.0 0    11.3   0.37    8,485                          9    0.8    B    200  21.6 0    11.6   0.48    7,370                          10   0.8    B    100  20.7 0    16.3   0.55   11,390                          11   0.8    B    200  22.3 0    16.7   0.48    8,030                          12   0.8    B    200  17.9 0.8  16.6   0.35   16,830                          13   0.8    B    200  21.7 0    19.3   0.55   10,230                          14    0.75  B    200  24.8 0    16.9   0.50    8,360                          15    0.85  B    200  25.6 0    --     0.50    9,430                          16   0.9    B    200  21.2 0    24.0   0.50   12,070                          17   0.8    B    200  23.4 0    17.2   0.55   10,000                          __________________________________________________________________________     *equivalents of maleic anhydride per mole of polyol.                          **moles of induced unsaturation per mole of polyol.                      

EXAMPLES 18-41

The products listed in Table II and III were prepared by procedure Bemploying the indicated polyols, monomers and concentrations.

                                      TABLE II                                    __________________________________________________________________________    Polyol D, g                                                                              Polyol B, g                                                                           Dodecanethiol, g                                                                       AN,                                                                              Sty,                                                                             Temperature                                                                          Viscosity                            Examples                                                                           Charge                                                                              Charge                                                                            Feed                                                                              Feed     g  g  °C.                                                                           cps, 25° C.                   __________________________________________________________________________    18   50    925  975*                                                                             10.5     260                                                                              790                                                                              90     2840                                 19   50    925 975 13.5     260                                                                              790                                                                              90     2830                                 20   50    925 975 13.5     260                                                                              790                                                                              95     2970                                 21   60    915 975 13.5     260                                                                              790                                                                              90     2910                                 22   50    925 975 10.5     260                                                                              790                                                                              90     coagulated                           23   50    925 975 13.5     260                                                                              790                                                                              90     3020                                 24   50    925 975 13.5     260                                                                              790                                                                              90     2750                                 25   60    885 945 14.0     278                                                                              832                                                                              90     3750                                 26   50    925 975 13.5     260                                                                              790                                                                              90     2700                                 27   10    185 195  2.1      52                                                                              158                                                                              90     2640                                 28   50    925 975 10.5     260                                                                              790                                                                              90     7380                                 29   75    900 975 10.5     260                                                                              790                                                                              90     6010                                 30   10    185 195  2.1      52                                                                              158                                                                              90     2860                                 31   50    925 975 10.5     260                                                                              790                                                                              90     --                                   32   50    925 975 13.5     260                                                                              790                                                                              90     3100                                 33   50    925 975 13.5     260                                                                              790                                                                              90     2900                                 34   50    925 975 12.5     260                                                                              790                                                                              90     3190                                 35   50    925 975 13.5     260                                                                              790                                                                              90     3100                                  36**                                                                              50    925 975 10.5     260                                                                              790                                                                              90     2860                                 37   50    925 975 14.5     260                                                                              790                                                                              90     2910                                 __________________________________________________________________________     g = grams                                                                     *3 gms methylbenzyldiphenylamine added.                                       **Initiator 2t-butylazo-2-cyano-4-methylpentane.                         

                                      TABLE III                                   __________________________________________________________________________    Polyol D, g                                                                              Polyol C, g                                                                           Dodecanethiol, g                                                                       AN,                                                                              Sty,                                                                             Temperature                                                                          Viscosity                            Examples                                                                           Charge                                                                              Charge                                                                            Feed                                                                              Feed     g  g  °C.                                                                           cps, 25° C.                   __________________________________________________________________________    38   10     185                                                                              195 2.1       52                                                                              158                                                                              90     3980                                 39   50    1000                                                                              105 9.0      225                                                                              675                                                                              90     3260                                 40   50    1000                                                                              105 9.0      225                                                                              675                                                                              90     2990                                 41   60     990                                                                              1050                                                                              9.0      225                                                                              675                                                                              90     3240                                 __________________________________________________________________________

EXAMPLES 42-93

Examples 48 and 52 were prepared by adding to a 500 ml flask fitted witha stirrer and a nitrogen inlet tube, 700 grams of polyol E and 0.7 gramsof morpholine. The reaction mixture was heated to 90° C. for 1 hour,then vacuum stripped for 30 minutes at 1 mm Hg pressure. Analysis bynuclear magnetic resonance showed 0.85 moles of fumarate unsaturation.This product was used in preparing the products of Examples 48 and 52.The remainder of the examples were prepared employing procedure D.

                                      TABLE IV                                    __________________________________________________________________________    Exam-                                                                             Polyol E, g                                                                         Polyol B, g                                                                            Dodecanethiol, g                                                                       AN, Sty,                                                                             Temperature                                                                          Viscosity                           ples                                                                              Charge                                                                              Charge                                                                            Feed Feed     g   g  °C.                                                                           csp, 25° C.                  __________________________________________________________________________    42  100   875 975  10.1     260 790                                                                              85     3350                                43  75    900 975  10.5     260 790                                                                              90     6760                                44  75    900 975  10.5     260 790                                                                              90     5840                                45  100   875 975  10.1     260 790                                                                              80     3050                                46  75    900 975  10.5     260 790                                                                              90     3340                                47  20    175 195  2.1*     52  158                                                                              90     3020                                48  20    175 195  2.1      52  158                                                                              90     3800                                49  100   845 945  11.1     278 832                                                                              90     4440                                50  75    900 975  10.5     260 790                                                                              90     4580                                51  75    900 975  10.5     260 790                                                                              90     5750                                52  75    900 975  10.5     260 790                                                                              90     12780                               53  75    705 117  10.5     260 790                                                                              90     3200                                54  100   845 945  11.1     278 832                                                                              90     3860                                55  75    900 975  10.5     260 790                                                                              90     7890                                56  20    175 195  2.1      42  168                                                                              90     3270                                57  20    175 195  2.1      52  158                                                                              90     3290                                58  100   875 975  10.5     260 790                                                                              90     3480                                59  100   875 975  10.5     260 790                                                                              90     3050                                60  20    175 195  2.1      21  189                                                                              90     36000                               61  20    175 195  2.1      63  147                                                                              90     7960                                62  40    350 390  4.2      104 316                                                                              90     11520                               63  20.6  160.4                                                                             180.1                                                                              2.4      60.1                                                                              180                                                                              75-119 5810                                64  20    175 195  2.1      52  158                                                                              90     4080                                65  20    175 195  2.1      52  158                                                                              90     4600                                66  20    175 195  2.1      52  158                                                                              90     4630                                67  10    185 195  2.1      52  158                                                                              90     6180                                68  20    175 195  2.1      52  158                                                                              90     3660                                69  20    175 195  2.6      52  158                                                                              90     4870                                70  15    180 195  2.1      52  158                                                                              90     3060                                71  15    180 195  2.1      52  158                                                                              90     3210                                72  75    900 975  10.5     260 790                                                                              90     3440                                73  100   875 975  10.5     260 790                                                                              90     3760                                74  100   875 975  10.5     260 790                                                                              90     3020                                75  100   550 1300 10.5     260 790                                                                              90     3600                                76  100   875 975  10.5     260 790                                                                              90     2910                                77  100   875 975  10.5     260 790                                                                              90     3250                                78  100   825 975  10.5     260 790                                                                              90     3300                                79  50.6  144.4                                                                             195.2                                                                              2.1      52  158                                                                              90     8900                                80  20.1  175 195.2                                                                              2.1      52  158                                                                              90     4010                                81  20.0  160 180  2.4      60  180.1                                                                            90     8170                                82  20    175 195  2.1      52  158                                                                              85     4410                                83  100   875 975  10.5     260 790                                                                              90     3540                                84  100   875 975  10.5     260 790                                                                              90     4130                                85  15    180 195  2.1      52  158                                                                              90     3620                                86  20    175 195  2.1      52  158                                                                              90     3500                                87  18    177 195  2.1      52  158                                                                              90     3340                                88  16    179 195  2.1      52  158                                                                              90     3300                                89  22    173 195  2.1      52  158                                                                              90     4000                                90  20    175 195  2.1      52  158                                                                              90     3440                                91  20    240 130  2.1      52  158                                                                              90     3320                                92  20    175 195  2.1      52  158                                                                              90     3300                                93  20    370 --   2.1      52  158                                                                              90     4500                                __________________________________________________________________________     *bromotrichloromethane used instead of dodecanethiol.                    

EXAMPLES 94-110

The products of Table V were prepared employing procedure E exceptproducts of Examples 111 and 112 where polyol E was replaced by polyolA.

                                      TABLE V                                     __________________________________________________________________________         Polyol E, g                                                                         Polyol B, g                                                                          Dodecanethiol, g                                                                       AN,                                                                              Sty,                                                                             Temperature                                                                          Viscosity                             Examples                                                                           Charge                                                                              Charge                                                                            Feed                                                                             Feed     g  g  °C.                                                                           csp, 25° C.                    __________________________________________________________________________     94  60    135 195                                                                              2.1      52 158                                                                              95     5340                                   95  70    160 190.4                                                                            1.8      45 135                                                                              90     3070                                   96  50    160 210                                                                              1.4      45 135                                                                              90     21200                                  97  49.9  160 210                                                                              1.8      45 135                                                                              90     2680                                   98  50    145 195.3                                                                            2.1      52 158                                                                              90     4260                                   99  60.1  134.9                                                                             195.1                                                                            2.1      52 158                                                                              90     4550                                  100  60    135 195                                                                              2.1      52 158                                                                              90     3940                                  101  60    135 195                                                                              1.6      52 158                                                                              90     5010                                  102  60    135 195                                                                              2.1      52 158                                                                              85     3960                                  103  300   675 975                                                                              10.5     260                                                                              790                                                                              90     4290                                  104  60    135 195                                                                              2.1      52 158                                                                              80     3560                                  105  60    135 195                                                                              1.9      52 158                                                                              90     3960                                  106  60    135 195                                                                              1.7      52 158                                                                              90     4020                                  107  60    135 195                                                                              2.3      52 158                                                                              90     3830                                  108  60    135 195                                                                              2.5      52 158                                                                              90     3830                                  109  60    135 195                                                                              2.1      52 158                                                                              90     5600                                  110  20    175 195                                                                              2.1      52 158                                                                              90     7270                                  __________________________________________________________________________

EXAMPLES 111-127

The polyurethane foams of Tables VI, VII and VIII were prepared bycharging a one quart cylindrical container with a suitable quantity ofthe polyol, water, catalysts, silicone surfactant and flame retardantcompounds. The mixture was stirred for about 30 seconds, allowed to setfor about 15 seconds and then stirring was resumed. After about 60seconds elapsed time, the polyisocyanate was added to the container, andthe resulting mixture was stirred for about 4 to 5 seconds. The contentof the container was then immediately poured into a cardboard cake box,and the foam was allowed to rise therein. After the foam rise wascompleted, the resulting foam was oven cured for about 15 minutes.

Tables VI, VII and VIII set forth the ingredients and amounts thereofused to prepare the foams as well as the physical properties of thefoams.

The flame retardancy tests, as exemplified by the California No. 117open flame test, indicate that flame retardancy may be obtained withreasonably low levels of flame retardant compounds employing the polymerdispersions of the instant invention.

                                      TABLE VI                                    __________________________________________________________________________    Example       111 112 113 114 115 116                                         Polyol        G   G   G   F   F   F                                           __________________________________________________________________________    Formulation, pbw                                                              Polyol        100.0                                                                             100.0                                                                             100.0                                                                             100.0                                                                             100.0                                                                             100.0                                       DE-71         6.0 6.0 6.0 6.0 6.0 6.0                                         THERMOLIN 101 3.0 6.0 12.0                                                                              3.0 6.0 12.0                                        REACTINT Blue X-44                                                                          0.25                                                                              0.5 1.0 0.25                                                                              0.5 1.0                                         Water         2.8 2.8 2.8 2.8 2.8 2.8                                         DABCO TL      0.11                                                                              0.11                                                                              0.11                                                                              0.11                                                                              0.11                                                                              0.11                                        T-10          0.4 0.4 0.4 0.4 0.4 0.4                                         DOP           0.8 0.8 0.8 0.8 0.8 0.8                                         TDI           37.1                                                                              37.1                                                                              37.1                                                                              37.1                                                                              37.1                                                                              37.1                                        Foam Properties                                                               Density, pcf  2.18                                                                              2.25                                                                              2.24                                                                              2.17                                                                              2.19                                                                              2.33                                        Tensile strength,                                                                           23.3                                                                              25.8                                                                              25.6                                                                              28.1                                                                              25.4                                                                              27.8                                        psi                                                                           Elongation, % 77  87  110 73  90  93                                          Tear, pi      2.4 2.3 3.1 2.0 2.1 2.5                                         Resilience, % 30  26  28  32  24  26                                          ILD, lb/50 sq. in. (4 inch)                                                   25%           118.0                                                                             112.0                                                                             102.0                                                                             124.0                                                                             116.4                                                                             110.0                                       65%           247.2                                                                             231.6                                                                             211.6                                                                             264.0                                                                             242.0                                                                             232.4                                       25% return    69.2                                                                              67.2                                                                              57.2                                                                              68.8                                                                              64.4                                                                              62.8                                        Sag factor    2.09                                                                              2.07                                                                              2.07                                                                              2.13                                                                              2.08                                                                              2.11                                        Guide factor  54.1                                                                              49.8                                                                              45.5                                                                              57.1                                                                              53.2                                                                              47.2                                        Recovery, %   59.0                                                                              60.0                                                                              56.0                                                                              55.0                                                                              55.0                                                                              57.0                                        50%           57.1                                                                              71.3                                                                              89.7                                                                              14.5                                                                              58.2                                                                              72.0                                        90%           81.1                                                                              95.7                                                                              98.0                                                                              83.4                                                                              95.8                                                                              96.8                                        Humid aged 5 hrs. at 250° F.                                           CLD, % of original 50%                                                                      61.1                                                                              71.0                                                                              74.0                                                                              80.0                                                                              84.0                                                                              79.0                                        Compression sets, %                                                           50%           57.4                                                                              66.9                                                                              87.0                                                                              25.4                                                                              57.7                                                                              66.1                                        90%           76.3                                                                              92.9                                                                              97.6                                                                              26.2                                                                              83.8                                                                              90.2                                        Heat aged 22 hrs.                                                                           29.6                                                                              31.8                                                                              31.6                                                                              31.5                                                                              33.0                                                                              34.9                                        at 284° F. tensile                                                     strength, psi                                                                 Air flow, cfm 0.80                                                                              0.86                                                                              0.45                                                                              1.92                                                                              1.10                                                                              1.10                                        Foam color    white       tan                                                 __________________________________________________________________________    Example       117 118 119 120 121 122                                         Polyol        G   G   G   F   F   F                                           __________________________________________________________________________    Water         2.8 2.8 2.8 2.8 2.8 2.8                                         DE-71         6.0 6.0 6.0 6.0 6.0 6.0                                         THERMOLIN 101 3.0 6.0 12.0                                                                              3.0 6.0 12.0                                        __________________________________________________________________________    CALIFORNIA NO. 117 SECTION A PART I - OPEN FLAME TEST                         __________________________________________________________________________                  Spec.                                                           Original      Max.                                                            Afterflame, sec.                                                              average       5.0  18.6                                                                             2.6                                                                              2.6                                                                             30.0                                                                              34.0                                                                             37.0                                        maximum       10.0 22.0                                                                             4.0                                                                              3.0                                                                             32.0                                                                              35.0                                                                             38.0                                        Char length, in.                                                              average       6.0   5.4                                                                             2.6                                                                              2.6                                                                             12.0                                                                              12.0                                                                             12.0                                        maximum       8.0   6.0                                                                             3.3                                                                              2.9                                                                             12.0                                                                              12.0                                                                             12.0                                        Heat aged 24 hrs./220° F.                                              Afterflame, sec.                                                              average       5.0  16.8                                                                             3.4                                                                              3.2                                                                             32.0                                                                              35.0                                                                             38.0                                        maximum       10.0 20.0                                                                             4.0                                                                              4.0                                                                             32.0                                                                              35.0                                                                             38.0                                        Char length, in.                                                              average       6.0   5.3                                                                             2.7                                                                              2.6                                                                             12.0                                                                              12.0                                                                             12.0                                        maximum       8.0   5.9                                                                             3.0                                                                              3.0                                                                             12.0                                                                              12.0                                                                             12.0                                        __________________________________________________________________________    CALIFORNIA NO. 117 SECTION D PART II -                                        SMOLDERING SCREENING TEST                                                     __________________________________________________________________________                  Spec.                                                                         Min.                                                            Non-smoldered 80.0 93.8  97.7                                                                            burned completely                                  residue, %                                                                    BUTLER CHIMNEY                                                                Weight retention, %                                                                              69.1                                                                             92.7                                                                             95.5                                                                            0   63.0                                                                             94.5                                        Flame height, cm   25+                                                                              22 19                                                                              25+ 25+                                                                              20+                                         __________________________________________________________________________    DOC FF-1-70 MENTHENAMINE PILL FLAME TEST                                      __________________________________________________________________________                  Spec.                                                                         Min.                                                            Inches burned >1   2.9                                                                              3.4                                                                              3.3                                                                             2.9 3.2                                                                              3.1                                         from outer ring                                                               OXYGEN INDEX                                                                  % O.sub.2          19.7                                                                             21.3                                                                             24.3                                                                            19.7                                                                              20.9                                                                             21.5                                        __________________________________________________________________________

                  TABLE VII                                                       ______________________________________                                        FLAME TEST DATA ON 30/70                                                      BLENDS OF POLYOL I/POLYOL H                                                   Example          123       124                                                ______________________________________                                        Formulation                                                                   Polvol I         30        30                                                 Polyol H         70        70                                                 Water            2.0       2.0                                                DEOA             0.8       0.8                                                L-5043           0.8       0.8                                                THERMOLIN 101    3.0       3.0                                                T-12             0.06      0.06                                               DABCO 33LV       0.18      0.18                                               NIAX A-1         0.06      0.06                                               TDI index        108       108                                                California No. 117 Section A Part I - Open Flame Test                                                  Spec.                                                                         Max.                                                 Afterflame, sec.                                                              average          0.7       0.7     5.0                                        maximum          0.8       0.8     10.0                                       Char length, in.                                                              average          2.1       2.3     6.0                                        maximum          2.2       2.5     8.0                                        California No. 117 Section D Part II - Smoldering Screening Test                                       Spec.                                                                         Min.                                                 Non-smoldered residue, %                                                                       86.4      89.0    80                                         ______________________________________                                    

                  TABLE VIII                                                      ______________________________________                                        Example         125        126     127                                        ______________________________________                                        Formulation                                                                   Polyol J        100.0      100.0   100.0                                      THERMOLIN 101   3.0        12.0    --                                         DE-71           --         --      12.0                                       ANTIBLAZE 19    --         --      5.0                                        Silicone L-5720 1.0        1.0     1.0                                        Water           2.4        2.4     2.4                                        DABCO TL        0.1        0.1     0.1                                        T-10            0.4        0.4     0.3                                        DOP             0.8        0.8     0.6                                        TDI (115 index) 32.5       32.5    32.5                                       Foam Properties                                                               Density, pcf    2.19       2.32    2.27                                       Tensile strength, psi                                                                         24.6       26.2    25.3                                       Elongation, %   70         127     100                                        Tear, pi        2.5        2.9     2.5                                        Resilience, %   26         30      32                                         ILD, lb/50 sq. in. (4 inch)                                                   25%             119.2      119.6   97.0                                       65              266.4      244.4   238.1                                      25% return      71.2       72.0    49.2                                       Sag factor      2.23       2.04    2.45                                       Guide factor    54.4       51.6    42.7                                       Recovery, %     60.0       60.0    51.0                                       Compression sets, %                                                           50%             25.4       82.4    73.9                                       90%             53.4       96.1    96.2                                       Humid aged 5 hrs. at 250° F.                                           CLD, % of original 50%                                                                        80.0       67.0    82.0                                       Compression sets, %                                                           50%             23.9       65.4    59.5                                       90%             27.7       95.6    92.5                                       Heat aged 22 hrs. at 284° F.                                                           33.5       30.6    30.1                                       tnesile strength, psi                                                         Air flow, cfm   0.53       0.50    0.50                                       Color            white                                                        CALIFORNIA NO. 117 SECTION A PART I -                                         OPEN FLAME TEST                                                                             Spec.                                                           Original      Max.                                                            Afterflame, sec.                                                              average       5.0     19.4      1.6  1.6                                      maximum       10.0    26.0      3.0  2.0                                      Char length, in.                                                              average       6.0     7.8       2.0  2.4                                      maximum       8.0     9.0       3.1  3.0                                      Heat aged                                                                     24 hrs./220° F.                                                        Afterflame, sec.                                                              average       5.0     15.2      1.4  1.2                                      maximum       10.0    21.0      3.0  2.0                                      Char length, in.                                                              average       6.0     6.5       2.3  2.8                                      maximum       8.0     8.7       3.1  3.1                                      CALIFORNIA NO. 177 SECTION D PART II -                                        SMOLDERING SCREENING TEST                                                                 Spec.                                                                         Max.                                                              Non-smoldered 80.0    96.6      99.2 99.9                                     residue, %                                                                    BUTLER CHIMNEY                                                                Weight retention, %                                                                             34.6      94.3   92.9                                       Flame height, cm  25+       17     14                                         DOC FF-1-70 MENTHENAMINE PILL FLAME TEST                                                  Spec.                                                                         Min.                                                              Inches burned >1      3.5          3.1                                        from outer ring                                                               ______________________________________                                    

The embodiments of the invention in which an exclusive privilege orproperty is claimed are defined as follows: .[.1. In a process for thepreparation of a white stable, low viscosity graft polymer dispersionwhich comprises the polymerization in a polyol mixture of from 5 to 60weight percent based on the total weight of the polymer dispersion of anethylenically unsaturated monomer, or mixture of said monomers, theimprovement which comprises conducting the polymerization in a polyolmixture containing from 0.001 to 0.09 mole of induced unsaturation permole of said polyol mixture..]. .[.2. In a process for the preparationof a graft polymer dispersion which comprises the polymerization of anethylenically unsaturated monomer or mixture of said monomers in thepresence of an effective amount of a free radical initiator in anunsaturation containing polyol mixture containing from 0.001 to 0.09mole of unsaturation per mole of polyol mixture, the improvement whichcomprises conducting the polymerization in an isomerized polyether-esterpolyol prepared by the reaction of a polyoxyalkylene polyether polyolwith maleic anhydride and an alkylene oxide..].
 3. In a process for thepreparation of polyether-ester polyols by the reaction of apolyoxyalkylene polyether polyol and a polycarboxylic acid anhydride toform a half acid ester followed by the reaction of the half acid esterwith an alkylene oxide to obtain a product having an acid number of lessthan 5 mg KOH/gm the improvement which comprises conducting the reactionbetween the polyether polyol and the anhydride and the followingreaction with the alkylene oxide in the presence of an effective amountof a catalyst selected from the group consisting of zinc, neodeconoate,calcium naphthenate, copper naphthenate and cobalt naphthenate.
 4. Awhite stable, .Iadd.low viscosity .Iaddend.graft polymer dispersioncomprising .[.a polymerized.]. .Iadd.from about 25 to 60 weight percentbased on the total weight of the polymer dispersion of an.Iaddend.ethylenically unsaturated monomer or mixture of monomers.Iadd.polymerized in situ .Iaddend.in a .Iadd.polyol .Iaddend.mixture.Iadd.initially .Iaddend.containing from 0.001 to 0.09 mole of inducedunsaturation per mole of said mixture.
 5. A white stable.Iadd., lowviscosity .Iaddend.graft polymer dispersion comprising .[.apolymerized.]. .Iadd.from 25 to 60 weight percent based on the totalweight of the polymer dispersion of an .Iaddend.ethylenicallyunsaturated monomer or mixture of monomers .Iadd.polymerized in situ.Iaddend.in .Iadd.a polyol mixture containing .Iaddend.a macromer saidmacromer prepared by the reaction of a conventional polyol with anorganic compound having both ethylenic unsaturation and a hydroxyl,carboxyl, anhydride, isocyanate or epoxy group said .[.macromer.]..Iadd.polyol mixture initially .Iaddend.containing from 0.001 to 0.09mole of induced unsaturation per mole of said .[.macromer.]..Iadd.polyol mixture.Iaddend..
 6. A white stable.Iadd., low viscosity.Iaddend.graft polymer dispersion comprising .Iadd.from about 25 to 60weight percent based on the total weight of the polymer dispersion of.Iaddend.a polymerized ethylenically unsaturated monomer or mixture ofmonomers in a polyol mixture .Iadd.initially .Iaddend.containing 0.001to 0.09 mole of unsaturation per mole of the polyol mixture wherein thepolyol mixture comprises an isomerized polyether-ester polyol preparedby the reaction of a polyoxyalkylene-polyether polyol with maleicanhydride and an alkylene oxide. .[.7. In a process for the preparationof a flame retardant polyurethane foam prepared by the reaction of anorganic polyisocyanate, a polyol, a blowing agent and flame retardantsthe improvement which comprises employing the graft polymer dispersionof claim 4..]. .[.8. In a process for the preparation of a flameretardant polyurethane foam prepared by the reaction of an organicpolyisocyanate, a polyol, a blowing agent, and flame retardants theimprovement which comprises employing the graft polymer dispersion ofclaim 5..]. .[.9. In a process for the preparation of a flame retardantpolyurethane foam prepared by the reaction of an organic polyisocyanate,a polyol, a blowing agent, and flame retardants the improvement whichcomprises employing the graft polymer dispersion of claim 6..]..Iadd.10. The dispersion of claim 4 wherein the viscosity of thedispersion is from 2000 to 8000 cps at 25° C. .Iaddend. .Iadd.11. Thedispersion of claim 4 wherein the monomer content is from about 30 toabout 45 weight percent based on the total weight of the polymerdispersion. .Iaddend. .Iadd.12. The dispersion of claim 5 wherein theviscosity of the dispersion is from 2000 to 8000 cps at 25° C. .Iaddend..Iadd.13. The dispersion of claim 5 wherein the monomer content is fromabout 30 to about 45 weight percent based on the total weight of thepolymer dispersion. .Iaddend. .Iadd.14. The dispersion of claim 6wherein the viscosity of the dispersion is from 2000 to 8000 cps at 25°C. .Iaddend. .Iadd.15. The dispersion of claim 6 wherein the monomercontent is from about 30 to about 45 weight percent based on the totalweight of the polymer dispersion. .Iaddend. .Iadd.16. A process for thepreparation of a white, stable, low viscosity, high solids content graftpolymer dispersion which comprises polymerizing in situ an ethylenicallyunsaturated monomer or a mixture of ethylenically unsaturated monomersin a polyol mixture containing from 0.001 to 0.09 moles of inducedunsaturation per mole of said polyol mixture in the presence of aneffective amount of a reaction moderator and a free radical initiator..Iaddend. .Iadd.17. The process of claim 16 wherein the solids contentis from 25 to 60 percent, based on the total weight of the dispersion..Iaddend. .Iadd.18. The process of claim 16 wherein the solids contentis from 30 to 50 percent, based on the total weight of the dispersion..Iaddend. .Iadd.19. The process of claim 16 wherein 55 to 100 weightpercent of the monomer is styrene. .Iaddend. .Iadd.20. The process ofclaim 16 wherein the viscosity is from 2000 to 8000 cps at 25° C..Iaddend. .Iadd.21. The process of claim 16 wherein the viscosity isfrom 3000 to 5000 cps at 25° C. .Iaddend. .Iadd.22. The process of claim16 wherein the polyol mixture contains an isomerized maleate-containingmacromer. .Iaddend. .Iadd.23. The process of claim 16 wherein the polyolmixture contains an isomerized maleate-containing macromer, wherein 55to 100 weight percent of the monomer is styrene, and wherein theviscosity is 3000 to 5000 at 25° C. .Iaddend. .Iadd.24. The process ofclaim 22 wherein the maleate-containing macromer is prepared in thepresence of a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.25.The process of claim 23 wherein the macromer is prepared in the presenceof a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.26. Theprocess of claim 24 wherein the divalent metal salt is calciumnaphthenate. .Iaddend. .Iadd.27. The process of claim 25 wherein thedivalent metal salt is calcium naphthenate. .Iaddend. .Iadd. The processof claim 16 wherein the polyol mixture contains a macromer prepared froma compound containing fumarate unsaturation. .Iaddend. .Iadd.29. Awhite, stable, low viscosity, high solids content graft polymerdispersion prepared by a process comprising polymerizing in situ anethylenically unsaturated monomer or mixture of ethylenicallyunsaturated monomers in a polyol mixture containing from 0.001 to 0.09moles of induced unsaturation per mole of said polyol mixture in thepresence of an effective amount of free-radical initiator and a reactionmoderator. .Iaddend. .Iadd.30. The product of claim 29 wherein thesolids content is from 25 to 60 percent, based on the total weight ofthe dispersion. .Iaddend. .Iadd.31. The product of claim 29 wherein thesolids content is from 30 to 50 percent, based on the total weight ofthe dispersion. .Iaddend. .Iadd.32. The product of claim 29 wherein 55to 100 weight percent of the monomer is styrene. .Iaddend. .Iadd.33. Theproduct of claim 29 wherein the viscosity is less than 10,000 cps at 25°C. .Iaddend. .Iadd.34. The product of claim 29 wherein the viscosity isfrom 3000 to 5000 cps at 25° C. .Iaddend. .Iadd.35. The product of claim29 wherein the polyol mixture contains an isomerized maleate-containingmacromer. .Iaddend. .Iadd.36. The product of claim 31 wherein the polyolmixture contains an isomerized maleate-containing macromer, wherein 55to 100 weight percent of the monomer is styrene, and wherein theviscosity is 3000 to 5000 at 25° C. .Iaddend. .Iadd.37. The product ofclaim 35 wherein the maleate-containing macromer is prepared in thepresence of a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.38.The product of claim 36 wherein the macromer is prepared in the presenceof a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.39. Theproduct of claim 37 wherein the divalent metal salt is calciumnaphthenate. .Iaddend. .Iadd. The product of claim 38 wherein thedivalent metal salt is calcium naphthenate. .Iaddend. .Iadd.41. Theproduct of claim 29 wherein the polyol mixture contains a macromerprepared from a compound containing fumarate unsaturation. .Iaddend..Iadd.42. The process of claim 3 wherein the catalyst is calciumnaphthenate. .Iaddend. .Iadd.43. A polyurethane foam characterized byflame retardancy prepared by a process comprising reacting the graftpolymer dispersion of claim 29 with an organic polyisocyanate. .Iaddend..Iadd.44. A polyurethane foam characterized by flame retardancy preparedby a process comprising reacting the graft polymer dispersion of claim30 with an organic polyisocyanate. .Iaddend. .Iadd.45. A polyurethanefoam characterized by flame retardancy prepared by a process comprisingreacting the graft polymer dispersion of claim 34 with an organicpolyisocyanate. .Iaddend. .Iadd.46. A polyurethane foam characterized byflame retardancy prepared by a process comprising reacting the graftpolymer dispersion of claim 35 with an organic polyisocyanate. .Iaddend..Iadd.47. A polyurethane foam characterized by flame retardancy preparedby a process comprising reacting the graft polymer dispersion of claim36 with an organic polyisocyanate. .Iaddend. .Iadd.48. A polyurethanefoam characterized by flame retardance prepared by a process comprisingreacting the graft polymer dispersion of claim 41 with an organicpolyisocyanate. .Iaddend.